CN110078596B - Recycling method of acetone in preparation of ethylhexyl glycerol - Google Patents
Recycling method of acetone in preparation of ethylhexyl glycerol Download PDFInfo
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- CN110078596B CN110078596B CN201811577033.7A CN201811577033A CN110078596B CN 110078596 B CN110078596 B CN 110078596B CN 201811577033 A CN201811577033 A CN 201811577033A CN 110078596 B CN110078596 B CN 110078596B
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- C07—ORGANIC CHEMISTRY
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D317/18—Radicals substituted by singly bound oxygen or sulfur atoms
- C07D317/22—Radicals substituted by singly bound oxygen or sulfur atoms etherified
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Abstract
A method for recycling acetone in the preparation of ethylhexyl glycerol comprises treating acetone obtained by distillation with dehydrating agent and organic acid, reacting with 2-ethylhexyl glycidyl ether at 35-45 deg.C in the presence of catalyst to obtain intermediate, adding anhydrous terminator at appropriate time, and filtering to remove solid residue formed by catalyst and terminator; and (3) treating the excess acetone distilled out from the filtrate under reduced pressure for recycling, adding acid into the residual system for hydrolysis reaction, and then neutralizing, washing and carrying out molecular distillation to obtain the high-purity daily chemical grade ethylhexyl glycerol. Realizes the recycling of acetone in the production process, is economic, safe and environment-friendly, and meets the requirement of industrial production.
Description
Technical Field
The invention belongs to the field of daily chemical preservatives, and particularly relates to a recycling method of acetone in preparation of ethylhexyl glycerin.
Background
The ethylhexyl glycerin is a novel multifunctional cosmetic additive with antiseptic effect and moisture retention and deodorization effects. Because the toxicological safety of the traditional preservative is under increasing doubt, the appearance of the ethylhexyl glycerin which is green, non-irritant and has the preservative effect brings hopes to people, and particularly, the ethylhexyl glycerin is used for a daily chemical product system by utilizing the synergistic effect of the ethylhexyl glycerin and other traditional preservatives, so that the addition amount of the traditional preservative can be greatly reduced, and the toxicity of the preservative system can be remarkably reduced. The preservative has preservative efficacy, has no stimulation to skin, is warm and moist, can enhance the preservative capability of the traditional preservative, and plays an important role in the 'no-additive' preservative.
Currently, ethylhexyl glycerol can be produced by etherification techniques, one is by catalytic opening of the epoxy group of ethylhexyl glycidyl ether for carbonyl addition with acetone, followed by hydrolysis; the second method is an addition reaction of an acid anhydride with a glycidyl ether followed by hydrolysis with a base. However, the latter is very easy to generate self-polymerization byproducts of glycidyl ether, has peculiar smell, low purity and color, and the subsequent refining and purification depends on the traditional rectification method and activated carbon decoloration, so the equipment investment is large, the cost is high, the purity is low, and the glycidyl ether can not be used as an additive of cosmetics and household care products. Therefore, the first method is a hotspot of the current development and production, acetone is a reactant and a solvent in the reaction, and has multiple functions of mass transfer and heat transfer, so that the acetone amount is excessive, and the recycling of the excessive acetone has important significance.
The applicant's earlier granted patent for invention "a process for preparing high purity ethylhexyl glycerol" (ZL 201510239933.0) relates to the synthesis of ethylhexyl glycerol by carbonyl addition,
although the above patent discloses that the excess acetone distilled off can be reused once, in practice, the repeated use of the ketone is of great practical significance because the terminating agent in the above patent contains water and enters the recovered acetone through the reduced pressure distillation part; meanwhile, the acetone is stored, so that the water in the air is easily absorbed in the treatment process; after multiple cycles, the water and other impurities are enriched and can not be recycled without treatment. For example, after 2 acetone recoveries, the chromatographic analysis shows that the content is only 97.1%, wherein the impurities comprise about 0.9% (weight percent) of water, alkyl glycidyl ether raw materials and light components brought in, intermediate 4-alkoxymethyl-1, 3-dioxoalkane, a small amount of heavy components and the like. The reaction conditions of primary acetone with alkyl glycidyl ethers have not been adapted to the recovery of acetone. Therefore, acetone needs to be specially treated to be matched with new process conditions for preparing the ethylhexyl glycerin to produce the high-quality ethylhexyl glycerin.
Acetone is a dangerous chemical and also a strictly regulated easy-to-prepare toxic chemical. The storage, transportation and use of the acetone-acetone composite material are strictly regulated, whether the acetone can be fully utilized is the most important factor for determining whether the production can be continuously carried out or not is considered from the requirements of environmental protection and safety, production cost control and atom economy, and the significance is great.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a recycling method of acetone in the preparation of ethylhexyl glycerol, and based on a method for preparing high-purity ethylhexyl glycerol in the patent ZL 201510239933.0, a recycling treatment method of acetone is provided, and the process in the past patent is improved, so that the high-purity ethylhexyl glycerol product is obtained, and meanwhile, the whole production process is almost free of organic matter emission, and the recycling method is safe, efficient, environment-friendly and sustainable in development.
In order to achieve the purpose, the invention adopts the technical scheme that:
a recycling method of acetone in the preparation of ethylhexyl glycerin is characterized by comprising the following steps:
1) treating the acetone obtained by distillation with 1% anhydrous potassium carbonate, and filtering;
2) adjusting pH value of the filtered acetone to 6.5-7.0 with 0.1-0.5% organic acid, and mixing the acetone and water at a weight ratio of 1: 1;
3) adding 2-ethylhexyl glycidyl ether and boron trifluoride diethyl etherate into the acetone solution obtained and treated by distillation, and reacting at 35-45 ℃ for 2 hours to generate a 4-alkoxymethyl-1, 3-dioxoalkane solution, wherein the molar mass ratio of the catalyst to the 2-ethylhexyl glycidyl ether is 1: 15-30, the molar mass ratio of the 2-ethylhexyl glycidyl ether to the acetone is 1: 3-10, and the mass ratio of the terminating agent to the boron trifluoride diethyl etherate is 1: 1;
4) a terminating agent is added thereto.
The terminating agent is methylamine gas or liquid ammonia.
The organic acid is boric acid or sorbic acid, and boric acid is preferred.
The acetone solution obtained and treated by distillation in the step 3) can be used alone for carbonyl addition reaction with 2-ethylhexyl glycidyl ether, or can be used by supplementing fresh acetone with a part of which the weight ratio is not more than 50 percent.
The invention has the beneficial effects that:
1) high purity: the purity of the ethylhexyl glycerin can reach more than 99.0 percent, and the ethylhexyl glycerin is colorless and tasteless;
2) high yield: the yield of the ethylhexyl glycerol calculated for the 2-ethylhexyl glycidyl ether reaches over 88 percent;
3) the water content in the recovered acetone is effectively controlled: after the anhydrous potassium carbonate treatment and the organic acid treatment are carried out, the moisture can meet the requirement of secondary reaction (the moisture content is less than 0.45 percent);
4) the addition of the anhydrous terminator can quickly terminate the reaction and prevent side reactions in the distillation process of the residual acetone, which is also important for controlling the color and luster; the acting terminator is easy to remove in a crystallization mode finally, and the purity of the product is not influenced; the terminator does not contain water, so that the water cannot be brought into acetone for recycling, which is different from terminators such as ammonia water or methylamine water solution used in earlier patents;
5) the organic acid treatment of acetone further optimizes the initiation conditions of the catalyst: the small amount of organic acid adjusts the treated acetone to be slightly acidic, which is beneficial to the initiation of the boron trifluoride diethyl etherate to the carbonyl addition reaction and simultaneously reduces the consumption of the catalyst, because the acidic boron trifluoride diethyl etherate can firstly neutralize the alkaline substances (small amount of ammonia, amine or potassium carbonate) in the recycled acetone, and can influence the initiation of the catalyst to the reaction although the amount is small; boric acid is preferred as the organic acid because boric acid and the terminator reactants are removed as a solid prior to acetone distillation without affecting the subsequent hydrolysis process.
6) The treatment process of the circulating acetone is simple: according to the reaction requirement, the acetone does not need rectification treatment, a small amount of impurities are allowed to exist, and the problem is solved by adjusting the reaction process;
7) the acetone is recycled without frequency limitation: by using the method, the acetone recycled is reused by adding fresh acetone if necessary (the amount of acetone obtained by each recycling can not reach the amount required by the process), and the recycling time is not limited.
8) The sustainable green process of the high-quality ethylhexyl glycerin is achieved by using the recycled acetone or the mixture of the recycled acetone and the fresh acetone and using a new terminator and a new process, and the large-scale production is easy.
Detailed Description
The invention is further illustrated by the following examples:
and (3) acetone recovery treatment: the residual acetone in the reaction is evaporated out under reduced pressure and placed in a container with stirring (can be collected in batches and then treated uniformly). Adding anhydrous potassium carbonate with the total weight of 1 percent, stirring for 50-80 minutes to ensure that the water content is less than 0.45 percent, standing and filtering; the filtered acetone is adjusted to pH 6.5-7.0 (test condition: acetone/water 1:1 weight ratio solution) with 0.1-0.5% organic acid (boric acid or sorbic acid), and then used for preparing the ethylhexyl glycerol.
If methylamine water solution or ammonia water is used as a terminator according to the prior patent ZL 201510239933.0, acetone obtained by distillation is difficult to be treated by anhydrous potassium carbonate to obtain acetone with the water content of less than 0.45%, therefore, methylamine gas or ammonia water is used in the method, and water is not generated in the process.
The following are examples of the production of ethylhexylglycerin, in which examples 1 to 4 used recovered acetone treated with potassium carbonate and boric acid; examples 5 and 6 use recovered acetone treated with potassium carbonate and sorbic acid.
Example 1
Adding 330 g of 2-ethylhexyl glycidyl ether into a 2000 ml four-neck flask provided with a mechanical stirrer, a thermometer and a dropping funnel, placing the flask in a water bath, controlling the temperature to be 35-40 ℃ under stirring, simultaneously dropwise adding 360 g of recovered acetone and 10 g of boron trifluoride diethyl etherate for 40 min, keeping the temperature for 80 min, adding 10 g of methylamine gas to keep the pH of a reaction solution at 7-8, keeping the pH for 10 min, filtering and precipitating, and distilling the filtrate under reduced pressure to obtain the residual acetone; adding 40 g of formic acid and 50 g of distilled water into the residual reactants, heating the mixture in a hot water bath to react for 180 minutes at 50-55 ℃, standing and separating the mixture, neutralizing an oil phase to be neutral by using sodium bicarbonate, washing the mixture twice, then carrying out short-path distillation, controlling the vacuum degree to be 40-50 Pa, collecting fractions with the distillation temperature of 135-145 ℃, and obtaining the high-purity ethylhexyl glycerin, wherein the purity is 99.2% and the yield is 88.1% through gas chromatography analysis, and the high-purity ethylhexyl glycerin is colorless and tasteless.
EXAMPLE 1 comparison 1 (distilled acetone without any treatment)
Adding 330 g of 2-ethylhexyl glycidyl ether into a 2000 ml four-neck flask provided with a mechanical stirrer, a thermometer and a dropping funnel, placing the flask in a water bath, controlling the temperature to be 35-40 ℃ under stirring, and simultaneously dropwise adding 360 g of acetone (untreated recovered acetone is circulated for 2 times) and 10 g of boron trifluoride diethyl etherate, wherein the reaction cannot be carried out (no thermal effect is generated); boron trifluoride diethyl etherate is added continuously until 30 g, 40 g and 50 g are not reacted. When 60 g of the additive is added, the instant reaction is initiated, the temperature cannot be controlled to 70 ℃, the mixture is rapidly boiled, the color is blackened, and the implementation is interrupted.
Example 1 comparative 2 (according to the reaction conditions of the previous patent ZL 201510239933.0)
330 g of 2-ethylhexyl glycidyl ether is added into a 2000 ml four-neck flask provided with a mechanical stirrer, a thermometer and a dropping funnel, the flask is placed in a water bath, the temperature is controlled to be 10-20 ℃ under stirring, 360 g of acetone (acetone recycled and treated by 3 times of circulation) and 10 g of boron trifluoride ethyl ether are added dropwise, and the reaction can not be carried out (no thermal effect is generated).
Example 2
The procedure of example 1 was repeated except for using 10 g of liquid ammonia as a terminator in place of methylamine in example 1 to obtain high-purity ethylhexyl glycerol of the present invention, which was analyzed by gas chromatography to have a purity of 99.3% and a yield of 88.2%, and was colorless and odorless.
Example 3 (application of recycled acetone to fresh acetone in a 1:1 weight ratio)
Adding 330 g of 2-ethylhexyl glycidyl ether into a 2000 ml four-neck flask provided with a mechanical stirrer, a thermometer and a dropping funnel, placing the flask in a water bath, controlling the temperature to be 35-40 ℃ under stirring, simultaneously dropwise adding 360 g of a mixture of recovered acetone and fresh acetone and 10 g of boron trifluoride diethyl etherate for 40 min, keeping the temperature for 80 min, adding 10 g of liquid ammonia, keeping the pH of a reaction solution at 7-8, filtering and precipitating after 10 min, and distilling the residual acetone from the filtrate under reduced pressure; adding 40 g of formic acid and 50 g of distilled water into the residual reactants, heating the mixture in a hot water bath to react for 180 minutes at 50-55 ℃, standing and separating the mixture, neutralizing an oil phase to be neutral by using sodium bicarbonate, washing the mixture twice, then carrying out short-path distillation, controlling the vacuum degree to be 40-50 Pa, collecting fractions with the distillation temperature of 135-145 ℃, and obtaining the high-purity ethylhexyl glycerin, wherein the purity is 99.4% and the yield is 88.1% through gas chromatography analysis, and the high-purity ethylhexyl glycerin is colorless and tasteless.
Example 4 (recovery of acetone using 12 cycles of work-up)
In a 2000 ml four-neck flask equipped with a mechanical stirrer, a thermometer and a dropping funnel, 330 g of 2-ethylhexyl glycidyl ether was added, the flask was placed in a water bath, temperature was controlled to 35 to 40 ℃ under stirring, and simultaneously, 360 g of 10 g of recovered acetone and boron trifluoride diethyl etherate which were subjected to 12 cycles of post-treatment were dropped for 49 minutes, followed by the procedure according to example 1, to obtain high-purity ethylhexyl glycerol of the present invention, which was analyzed by gas chromatography, had a purity of 99.2%, a yield of 88.0%, and was colorless and odorless.
Example 5
360 g of recovered acetone treated with potassium carbonate and sorbic acid was used in place of the recovered acetone treated with potassium carbonate and boric acid in example 1. The sorbic acid and the terminating agent form ammonium salt dissolved in the system, so that the ammonium salt cannot be separated as a solid before the residual acetone in the system is distilled out, and enters a hydrolysis reaction step under an acidic condition, but the amount is small enough not to influence the hydrolysis reaction.
The other conditions were the same as in example 1. The obtained high-purity ethylhexyl glycerol has the purity of 99.1 percent and the yield of 88.4 percent through gas chromatography analysis, and is colorless and tasteless.
Example 6 (adjustment of the Water content of the recycled acetone to 0.6% in the Recycling Process)
Adding 330 g of 2-ethylhexyl glycidyl ether into a 2000 ml four-neck flask provided with a mechanical stirrer, a thermometer and a dropping funnel, placing the flask in a water bath, controlling the temperature to be 35-40 ℃ under stirring, and simultaneously dropwise adding 360 g of acetone (treated recovered acetone, the water content of the acetone is adjusted to be 0.6%) and 10 g of boron trifluoride diethyl etherate, wherein the reaction can not be carried out (no thermal effect is generated); boron trifluoride diethyl etherate is continuously added to 40 g, and the reaction is initiated. The subsequent process followed example 1 gave ethylhexylglycerin which, by gas chromatography, had a purity of 85.1%, a yield of 71.4%, yellow color with off-flavor and was not used as a cosmetic additive.
Claims (2)
1. A recycling method of acetone in the preparation of ethylhexyl glycerin is characterized by comprising the following steps:
1) treating the acetone obtained by distillation with 1% anhydrous potassium carbonate, and filtering;
2) adjusting pH of the filtered acetone to 6.5-7.0 with 0.1-0.5% boric acid or sorbic acid;
3) adding 2-ethylhexyl glycidyl ether and boron trifluoride ethyl ether into the acetone solution obtained and treated by distillation, and reacting at 35-45 ℃ for 2 hours to generate a 4-alkoxymethyl-1, 3-dioxoalkane solution, wherein the molar mass ratio of boron trifluoride ethyl ether to 2-ethylhexyl glycidyl ether is 1: 15-30, and the molar mass ratio of 2-ethylhexyl glycidyl ether to acetone is 1: 3-10;
4) adding a terminating agent thereto; the terminating agent is methylamine gas or liquid ammonia, and the mass ratio of the terminating agent to boron trifluoride diethyl etherate is 1: 1.
2. The method of claim 1, wherein the acetone solution distilled and treated in step 3) can be used alone for carbonyl addition reaction with 2-ethylhexyl glycidyl ether or can be used in combination with fresh acetone in an amount of not more than 50% by weight.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101190879A (en) * | 2007-12-21 | 2008-06-04 | 天津大学 | Magnetization rectification method for reclaiming acetone from waste acetone menstruum |
| CN101812075A (en) * | 2010-05-07 | 2010-08-25 | 郝志艳 | Cefixime compound and novel preparation method thereof |
| CN101898765A (en) * | 2010-07-30 | 2010-12-01 | 淮阴工学院 | Method for effectively dispersing depolymerization and preventing secondary agglomeration of attapulgite clay crystal bundle |
| CN104817436A (en) * | 2015-05-13 | 2015-08-05 | 陕西省石油化工研究设计院 | Method for preparing high-purity ethylhexylglycerin |
| CN107216240A (en) * | 2017-07-24 | 2017-09-29 | 湖北阿泰克生物科技股份有限公司 | A kind of synthetic method of Sensiva SC50 |
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- 2018-12-23 CN CN201811577033.7A patent/CN110078596B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101190879A (en) * | 2007-12-21 | 2008-06-04 | 天津大学 | Magnetization rectification method for reclaiming acetone from waste acetone menstruum |
| CN101812075A (en) * | 2010-05-07 | 2010-08-25 | 郝志艳 | Cefixime compound and novel preparation method thereof |
| CN101898765A (en) * | 2010-07-30 | 2010-12-01 | 淮阴工学院 | Method for effectively dispersing depolymerization and preventing secondary agglomeration of attapulgite clay crystal bundle |
| CN104817436A (en) * | 2015-05-13 | 2015-08-05 | 陕西省石油化工研究设计院 | Method for preparing high-purity ethylhexylglycerin |
| CN107216240A (en) * | 2017-07-24 | 2017-09-29 | 湖北阿泰克生物科技股份有限公司 | A kind of synthetic method of Sensiva SC50 |
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